Alkylation process



Feb. 18, 1958 J. T. KELLY ETAL 2,824,153

ALKYLATION PROCESS Filed June 13, 1956 A 6 T/ONA Bottoms SEPARATOI?REACTOR INVENTORS Joe 71' Kelly Harman M. Knight ATTORNEY United StatesPatent ALKYLATION PROCESS Joe T. Kelly, Dickinson, and Harmon M. Knight,La Marque, Tex., assignors to The American Oil Company, Texas City,Tex., a corporation of Texas Application June 13, 1956, Serial No.591,040

13 Claims. (Cl. 260-68344) moms. One of the remaining sources of highoctane components is the product of the alkylation of isobutane andethylene. This alkylation is not easy to carry out, particularly on alarge scale.

An object of the invention is the alkylation of isoparaffins,particularly isobutane, with olefins, particularly ethylene. Anotherobject is the alkylation of aromatic hydrocarbons with olefins. Otherobjects will become apparent in the course of the detailed description.

The alkylation of isoparatfins or aromatic hydrocarbons with olefins iscarried out in the presence of a novel catalyst pair. One member oi thecatalyst pair is boron trifludrid'e. The other member of the catalystpair is a inetjal pyroantimonate hydrate, that is a metal pyroantimonatesalt containing water of hydration. Although the second component of thecatalyst pair is spoken oi as a metal pyroantimonate hydrate, it isbelieved that the solid member is more properly a complex of thehereinafter defined metal pyroantimonate hydrate and BF the BF, isbelieved to complex with some or all of the hydrate water present in themetal pyroantimonate hydrate salt. More than the amount of 'BF needed tocomplex the water of hydration is necessary to obtain the desiredcatalytic effect.

Boron trifiuoride is one member of the catalyst pair. Commercial gradeanhydrous boron trifiuoride is suitable for use as one member of thecatalyst pair.

The other member of the catalyst pair, hereinafter spoken of as thesolid member, is a metal pyroantimonate hydrate, i. e., a metalpyroantimonate salt containing water of hydration. The salt may be usedas a fine powder, as pellets, or may be supported on a solid carriersuch as alumina, charcoal, silica gel, etc. Not all metalpyroantimonateswhich contain water of hydration are suitable, nor are all metal ionssuitable. The particular metal ion components of the pyroantimonate salthydrates are cadmium, ferric, magnesium, mercury, nickelous andpotassium dihydrogen. In determining the effective members, it has beenconsidered that the catalyst pairs which did not produce a yield, on aweight percent basis on ethylene charged, when isobutane and ethylenewere contacted, of 100% or more, were unsuitable.

It is necessary that the above-defined salts contain hydrate water. Theanhydrous salts do not have any promotional effect on the activity ofBF;,. .In those cases wherein a salt may exist in forms having variousamounts of water of hydration present, it is not necessary that anyparticular hydrate be used. Apparently it is necessary only that somewater of hydration'be present.

The BF and the defined salt react to form a solid ma terial containingcomplexed BF Whenthesalt hydrate 2,824,158 Patented Feb. 18, 1 958 andBF;, are contacted in a closed vessel, the BE, partial pressure dropsvery rapidly at first and then gradually approaches a constant value. Itappears that a very rapid reaction between the BF and some of the waterof hydra tion takes place. This initially rapid reaction is thenfollowed by a relatively slow reaction between the remaining moleculesof hydrate water and additional BB It appears that when the salt hydrateis exposed to 3P even in the presence of hydrocarbon reactants,eventually by the formation of alkylate, even though all of the hydratewater has not been complexed. In a batch system, whereinless BF,ispresent than is theoretically required to complex all the water ofhydration present in the salt hydrate, eventually no alkylation willoccur as charge is added, since all of the BE, will become complexed.

Ingeneral, the process is carried out utilizing an amount of BB; whichis in excess of that required to complex with all thehydrate. waterpresent in the contacting zone, namely, in excess of about 1 mole of BF,per mole. of hydrate water present. More than the minimum amount.oftree-BF; is beneficiahin fact, the yield of alleylateim creasesrapidly withincrease in free-BF, present, up to a ma i m am ntusage isdesirably, set out on a BB to olefin weig ht ratio, of at least about0.2. In other words, at ,leastabout 0.2? lb. of free-BF per lb. ofolefin charged to the alkylation zone is desirable. About 1.5 parts. byweight of ,BE per part of olefin charged appears to be about the desisgable maximum usage of BB. It is preferred to use between about 0.35and 1 part by weight of tree-Bfi-perpartby weight of olefin Whenutilizing the, lower molecular weight olefin, such as ethylene andpropylene.

The process may be carried out at. any ;.temp ertature below thetemperatures: which the salt shydrate decomposes, that is, loss of allits water of .hydration. The temperatures of operation may be as lower..--20 .C. or even lower. Temperatures as high a s l;5 0- C. andevenhigher may beused with some of the salt hydrateswhich have relatively,highdecornposition temperatures More usually the temperature of operationwill be'betweenabout 0 C. and C. Lower temperaturesappeartofavor the formation of the hydrocarbons having6 to 7 carbonatoms. It is preferred to operateat atempenaturebetween about 25 C. and40 C.

Sutficient pressure is maintained on .the system. to keep a. substantialportion of the hydrocarbons chargeduinrthe liquid state. The process maybetcarried outat relatively low pressures, forexample, 100 p. s. i.,ortitmay becarried out at elevated pressures, for example, 2000 p. s.i., or more. In general, pressures will be betweenabout 2 00 and 1000 p.s. i. andprefejrably between ab ut300 and 600 p. s. i. r

The contacting of theisoparafiin or aromatichydrocarbon and the olefinin the presence of the defined c atalyst pair is continued until anappreciable amount of allgylate has been formed. In batch reactions, itis possibleqtoyib tually extinguish the olefin, i. e., convertessentially 100 of the olefin by asufiicientlylong periodiof contacting.

When operating in-acontinuous flow system, it may be,

The amount of free- 3F, ,used is. dc.- pendent somewhat upon thereactants themselyes. How-- ever, when reacting isoparafrins andolefins, the tree Blk desirable to have a time of contacting such thatsub stantial amounts of olefin are not converted and obtain the completeconversion of the olefin by a recycle operation. The time of reactionwill be determined by the type of hydrocarbons charged, the ratio ofisoparafiin or aromatic to olefin, the degree of mixing in thecontacting zone and the catalyst usage. A few testswill enable one todetermine the optimum time of contacting for the particular system ofoperating conditions being tried.

The reactants in the hydrocarbon charge to the alkylation process areisoparafiin, or aromatic and olefin. The olefin contains from 2 to about12 carbon atoms. Examples of suitable olefins are ethylene, propylene,butene-Z, hexene and octene; in addition to these, the olefin polymersobtained from propylene and/or butylene are also suitable for use in theprocess, such as codimer, propylene trimer, propylene tetramer andbutylene trimer. It is preferred to operate with ethylene or propylene.

The aromatic hydrocarbons must be alkylatable by the particular olefinused. It is self-evident that an aromatic hydrocarbon which containsalkyl substituents positioned so that steric hindrance would prevent orgreatly reduce the possibility of alkylation with the particular olefinshould not be subjected to the process. Examples of particularlysuitable aromatic hydrocarbons are benzene, toluene, xylene,trimethylbenzenes, and the other alkyl analogues, such as propyl andbutyl; the naphthalene aromatic hydrocarbons, such as the mono anddisubstituted methylnaphthalenes.

The isoparafiin reactant is defined as a paraflinic hydrocarbon whichhas a tertiary hydrogen atom, i. e., parafiins which have a hydrogenatom attached to a tertiary carbon atom. Examples of these areisobutane, isopentane, (2- methylbutane), Z-methylpentane,Z-methylhexane, 3- methylhexane, 2,3-dimethylbutane (di-isopropyl) and2,4- dimethylhexane. Thus the isoparafiins usable as one reactant in theprocess contain from 4 to 8 carbon atoms.

In the-isoparatfin-olefin system, the alkylation reaction is morefavored as the mole ratio of isoparaffin to olefin increases. Ingeneral, the isoparafiin to olefin mole ratio in the hydrocarbon chargeshould be at least 1. More than this amount is good and it is desirableto have an isoparafiin to olefin ratio between about 2 and 25 and insome cases more, for example, as much as 50. It is preferred to operatewith an isoparaflin to olefin mole ratio of between about 5 and 15.

The presence of non-reactive hydrocarbons in the hydrocarbon charge isnot detrimental unless the reactants become excessively diluted. Forexample, the isoparafiin may also contain isomers of the normalconfiguration. The olefins may contain parafi'ins of the same carbonnumber. Mixtures of 2 or more isoparatfins or 2 or more aromatichydrocarbons, or 2 or more olefins may be charged. In general, when aparticular product distribution is desired, it is preferable to operatewith a single isoparaffin and a single olefin, for example, technicalgrade isobutane and ethylene, both of about 95% purity.

The reactants may be mixed together before they are charged into thereactor. Or, they may be charged into the reactor separately. Or, aportion of the olefin may be blended with the isoparafiin or aromaticbefore introduction into the reactor and the remainder of the olefininjected into the reactor. The charge may be introduced all at one pointinto the reactor or it may be introduced at 2 or more points. Thealkylation reaction is somewhat exothermic and temperature control isfacilitated by introducing the olefin into the reactor at more than onepoint.

The 8P member of the catalyst pair may be premixed with the isoparaffinand olefin before introducing these into the reactor but this should notbe done when an extremely reactive system such as isobutanes andisobutylene or aromatic hydrocarbons and olefins are being used; or whenan olefin that is very rapidly polymerizable is being used. The BF maybe blended with the isoparaflin reactant and introduced into the reactorwith this member when the isoparaffin and the olefins are beingintroduced separately. The BF may also be introduced directly into thereaction zone independently from the hydrocarbons charged. The BB, maybe introduced into the reactor at a single point or at several points tohelp control temperature and reaction rate.

The reactor may be a vessel providing for a batch-type reaction, i. e.,one wherein the desired amount of isoparaffin or aromatic and olefin arecharged to a closed vessel containing the catalyst pair and the vesselthen maintained at the desired temperature for the desired time. At theend of this time, the hydrocarbon product mixtureand unreacted materialsare withdrawn from the vessel and processed to separate the alkylateproduct from the unreacted materials and lower and higher molecularweight materials. The reactor may be a fixed bed type wherein thereactants and free-BF} are flowed through the bed of the hydrate saltmember of the catalyst pair the space velocity being controlled so thatthe desired amount of reaction is obtained during the passage of thereactants through the bed of hydrate salt. Under some conditions, amoving bed of hydrate salt may be utilized. In still another set ofcircumstances, a fluidized bed of hydrate salt may be utilized with theincoming stream of reactants providing the energy for the fluidizationof the solid hydrate salt. Other methods of operation common in thecatalytic refining aspects of the petroleum industry utilizing solidcatalyst may be readily devised.

It has been pointed out that the solid member of the catalyst pair isreally a complex of the metal salt hydrate and BF the BF apparentlyreacting with the water of hydration. The complex may be preformed, byexposing the salt hydrate to BF for a time suflicient to introduce someBF into the solid component or even enough to complex all. of the waterof hydration; this being done before the reactants are introduced intothe reaction zone or even before the solid member of the catalyst pairis positioned in the reaction zone. The complex may be formed in situduring a batch-type reaction.

'In the batch-type operation, it is convenient to introduce all the BFinto the reaction vessel at once. This amount of HE, is sufficient notonly to complex with the water of hydration but also provide the desiredamount of free-B1 In a flow system, the solid member may be prepared insitu by charging fresh hydrate salt to the reaction zone and forming thecomplex during the initial passage of reactants and BF over the salthydrate. Some alkylation reaction occurs even though the salt hydratehas not taken up suflicient BF to complex all the water of hydration. Asthe flow of reactants and BF; continues over the solid member,eventually the salt hydrate will become saturated with respect to BF Atthis time the amount of BF introduced into the reaction zone should becut back to that amount of free-BF desired, under this particular set ofoperating conditions.

The illustrative embodiment set out in the annexed figure forms a partof this specification. It is pointed out that this embodiment isschematic in nature, that many items of process equipment have beenomitted, since these may be readily added by those skilled in this artand that this embodiment is only one of many which may be devised, andthat the invention is not to be limited to this particular embodiment.

In this embodiment, it is desired to produce a high yield ofdi-isopropyl for use as a blending material for gasoline. Ethylene fromsource 11 is passed by way of line 12 into mixer 13. Liquid isobutanefrom source 14 is passed by way of lines 16 and 17 into mixer 13. Boththe ethylene and the isobutane are about purity, the remainder beingn-butane and ethane, with trace amounts of other components found inmaterials derived from petroleum refining sources. Mixer 13, in thisinstance, is a simple orifice-type mixer suitable for intermingling aliquid and a gas, or two liquids. Recycle enemas isobutane from line 18is passed by way of line 17 into mixer 13. In this embodiment, the molarratio of isobutane to ethylene is 6.

From mixer 13, the blend of isobutane and ethylene is passed by way ofline 19, through heat exchanger21, where the temperature of the blend isadjusted to 30 C. The temperature of the. blend leaving. exchanger 21 issomewhat lower than the reaction temperature, since there is a heat risein the reactor due to exothermic reaction. From exchanger 21, the streamof isobutane and ethylene is passed by way of lines 22 and 23 into thetop of reactor 24.

Boron triiluoride is passed from source 26 by way of valved line 27 andline 28 into line 23, where itmeets the stream of isobutane andethylene. If desirable, a mixer may be introduced into line 23 to insurecomplete intermingling of the BF and the hydrocarbon charged. Recycle BFis introduced from line 29 by way of lines 28 and 23. In thisembodiment, the salt hydrate is completely complexed with respect to BFand only the necessary free-B1 is introduced by way of line 28. Theweight ratio of free-BF from line 28 to ethylene present in line 23 is1.1

Reactor 24 is shown as a shell and tube type vessel. Hydrate salt iscontained in the tubes 31. The alumina balls 32 and 33 are positionedabove and below the headers in the reactor to maintain the hydrate salewithin the tubes. In order to maintain the temperature in the reactor atsubstantially 35 C., water is introduced into the shell side by way ofline 36 and is withdrawn by way of line 37.

In this embodiment, the reactor was charged with Ni Sb O .3H O. Thehydrate saltwas preformed into pellets from one-eighth inch in diameterand. aboutoneeighth inch in height. Some silica was present to act as alubricant in the extrusion of thepellets. The salt hydrate was contactedwith BF in an amount such that all of the water of hydration wascomplexed with BF This operation was carried out before ractants wereintroduced into the reactor. The reactor pressure was maintained at 600p. s. i. Thispermits maintaining the isobutane and substantially all ofthe ethylene in the liquid state.

The product hydrocarbon mixture is passed out of reactor 24 by way ofline 41. This stream contains the alkylate product,.unreacted isobutane,asmallamount of unreacted ethylene and pentanes as well as BF The streamfrom line41 ispassed into gas separator 42 where the BF isobutane, somepentanes and some. alkylate product are taken overhead by way of. line43. The material taken overhead from the separator. 42 is. passed intofractionator 44.

Fractionator 44 is adapted to separate the BE, as. a gas, the isobutaneas a liquid and the higher boiling materials as a bottoms product.Fractionator 44 is provided with an internal reboiler 46 and an internalcondenser 47. 3P and unreacted: ethylene are taken overhead fromfractionator 44 by way of line 48 and may be passed out ofthe system byway of valve line 49. The materialafrom line 49 may be periodicallypassed to a- BF purification operation to remove non-condensable inertgases which build up in the system. Ordinarily the stream from line 48is recycled by way of valved lines 29 and lines 28 and 23 to reactor 24.

isobutane is withdrawn as a liquid stream by way of line 51 and isrecycled by way of lines 18 and 17 to mixer 13-for reuse in the process.Bottoms product from fractionator 44 is withdrawn by way of line 52 andmay be passed to storage or further processing by way of valved line 53.This stream from line 52 consists substantially of isopentane. Someunsaturated C hydrocarbons are also present and also a small amount ofhigher boiling alkylate material.

The liquids separated in gas separator 42 are passed by way of line 56into fractionator 57. The bottoms 6 product from fractionator 44 may bepassed by way of valved line 58 and line. 56 into fractidnator 57 forcomplete removal of the alkylate material. In thisem bodiment, thebottoms are passed to fractionator 57.-

Fractionator 57 is provided. with an internal reboiler 58 and is adaptedto produce the desired alkylate products from the hydrocarbon productmixture entering from line 56. A vapor stream is taken overhead by wayof line 61, is condensed in cooler 62 and is passed to storage by way ofline 63. The material from line 63 consists substantially of isopentaneand some unsaturated C material. This material may be used as a highoctane blending stock for the production of motor gasoline of thedesired volatility characteristics.

The alkylate product herein is considered to be that boiling above thepentane' range and" boiling below the maximum temperature usable inmotor gasoline. In general, a 415 F. endpoint alkylate is blendable intomotor gasoline without adverse eilect. in at specification calling for a400 F. gasoline endpoint. Thus the. alkylate product is considered to bethe. material boiling between about'the lower limit of the hexane rangeand 415 F. in the ASTM distillation procedure.

A considerable difference exists between the octane number of the Cfraction of the alkylate product and the higher boiling material. The Cfraction, which boils from about 110 to170" F., has an F-l octane numberof 101. The C material has an octane number which ranges between about75 and 85, depending somewhat on the fractionation.

Light alkylate, which includes all the C material and some of the 0,material, is withdrawn from fractionator 57 by way of line 66. Heavyalkylate, which includes most of. the C and material boiling up to 415F. is withdrawn from fractionator 57 by way of line 67. A small amountof higher boiling bottoms is withdrawn by way of line 68.

In general, the C fraction of the alkylate product will contain fromabout 86 to about 90 mole percent of diisopropyl (2,3-dimethylbutane).Z-methylpentane and 3-methylpentanerepresent substantially the remainderof the C product; Generally, only trace amounts of n-hexane are present.

The results obtainable by the process of the instant invention are setout in illustrative runs below.

In Tables I and II, there are set out results in the testing of variousmetal pyroantimonate hydrates by means of batch operation. In theseruns, the tests were carried out under what are more or less standardconditions, namely, a 4-liter carbon steel. bomb was dried overnight ina stream of hot air at C. Thesalt to be tested (90 grams) was charged.to the bomb as a powder and the. bomb was evacuated. One kilogram of adry blend of ethylene and isobutane was added and then BE, (90 grams)was pressured in. The'charged bombs were placed in a rocker and allowedto rock for 20 hours. At the end of this time a liquid sample was drawnthrough a bomb containing activated alumina (to remove dissolved BF andsalt particles)... This sample was submitted for Podbielniakdistillation.

A C cut from the Podbielniak distillation was analyzed by massspectrometer. In some cases after sampling, the remaining major portionof the product was debuta nized on an Oldershaw column and thenfractionated on a packed column.

In Table I, run No. 1 was carried out as described above except that nosalt was present in the bomb. The results show that only 34% ofdepentanized alkylate product was obtained by the use. of BF alone asthe catalyst. Run No. 2, carried out with anhydrous potassium dihydrogenpyroantimonate and BF was worse than BF alone. Run No. 3,, usingpotassium dihydrogen pyroantimonate hydrate asthe promoter, produced adepentanized alkylate product yield of 167%, based on ethylene charged.

In Table No. II, there are set out the results Of testing various metalpyroantimonate hydrates. These data were obtained under the approximatestandard conditions utilized in bomb work. These standard conditions areapproximately: Isobutane-ethylene mole ratio, 2.4; hydrocarbon/saltweight ratio, 11; BF /ethylene weight ratio, 0.7; 20 hours contactingtime, temperature range, 2035 C. and an initial pressure of about 350 p.s. 1. g.

TABLE I Run No 1 2 3 Pyroantimonate None K211231201 K:H:SbzO1.4H|O

Conditions:

Isobutane/Etbylene (Molar). 3.0 3.0 2. 6 Hydrocarbon/Salt (Weight). 10.7 11. 4 BFa/Ethylene (Welght) 0.7 0.6 0. 7 Time, Hours 20 20 20 7Temperature. C 25-35 20-25 15-20 Pressure (Range). 9. s. i. g 300300-280 310-98 Results:

Alkylate (Depentanized) (wt. percent)- Pentanes 6 0 Hexanes 21 9 89 0 137 78 Total 34 16 167 Ethylene Converted, Percent 91 1 Podbielniak andmass spectrometer analyses, based on ethylene charged.

TABLE II Various pyroantimonate hydrates Run N o 3 4 5 6 7 8 9 PotassiumCadmi- Magnesi- Manga- Cation Present Dihygro' Ferric um um Mercurynose- N lcke1 gen Moles of Water of Hydratiom- 4 5-6 3 2 1 3 3 EthyleneConverted, Percent 91 94 80 79 90 74 98 Alkylate (Wt. Percent:

Isopentane 0 10 0 16 27 17 11 Hexanes 89 58 51 41 27 54 95 Total (05Free) 167 112 125 111 120 98 162 1 Podbielniak and mass spectrometeranalyses, based on ethylene charged.

Thus having described the invention what is claimed is: p 1. Analkylation process comprising contacting (a) an alkylatable feedhydrocarbon from the class consisting of (1) isoparafiin having from 4t0 8 carbon atoms and (2) aromatic hydrocarbon and (b) an olefin havingfrom 2 to 12 carbon atoms, in the presence of a catalyst comprisingessentially (i) a metal pyroantimonate salt containing water ofhydration, the metal ion of said salt being from the class consisting ofcadmium, ferric, magnesium, mercury, nickelous and potassium dihydrogenand (ii) BF said BF being present in an amount in excess of about 1 moleper mole of water of hydration in said salt, at a temperature betweenabout -30 C. and a temperature substantially below the temperature atwhich said hydrate salt decomposes, and at a pressure sufficient tomaintain a substantial portion of said reactants in the liquid state,and separating a hydrocarbon product mixture containing alkylate productof said feed hydrocarbon and said olefin.

2. An alkylation process wherein an isoparaflin having from 4 to 8carbon atoms and an olefin having from 2 to 12 carbon atoms arecontacted, in a molar ratio of isopar afiin to olefin between about'2and 50, at a temperature between about 20 C. and 150 C. and a pressurebetween about 100 and 2000 p. s. i., said pressure being at leastsufficient to keep a substantial portion of said react ants in theliquid. state, for a time sufiicient to permit an appreciable amount ofalkylation reaction to take place, in the presence of a catalystcomprising essentially (i) a metal pyroantimonate salt containing waterof hydra- 3. The process of claim 2 wherein said isoparaflin isisobutane.

4.- The process of claim 2 wherein said isopraraffin is di-isopropyl.

5. The process of claim 2 wherein said olefin is ethylene.

6. The process of claim 2 wherein said olefin is propylene tetramer.

7. The process of claim 2 wherein said salt is potassium dihydrogenpyroantimonate.

8. The process of claim 2 wherein said salt is nickelous pyroantimonate.

9. The process of claim 2 wherein said temperature is between about 25C. and 40 C.

10. The process of claim 2 wherein the BF is present in an amount, inexcess of 1 mole per mole of hydrate water, such that the 'free-BF toolefin weight ratio is between about 0.2 and 1.5.

11. An 'alkylation process which comprises contacting isobutane andethylene in a molar ratio of isobutane to ethylene between about 2 and25 at a temperature between about 20 C.'and C. at a pressure betweenabout 200 and 1000 p. s. i., said pressure being sufficient to keep asubstantial portion of said reactants in the liquid state-for a timesuflicient to permit an appreciable amount of alkylation reaction totake place, in the presence of a catalyst 'pair comprising essentially(a) a salt BF complex consisting of a metal pyroantimonate saltcontaining water of hydration, the metal ion component being selectedfrom the class consisting of cadmium, ferric, magnesium, mercury,nickelous and potassium dihyd'rogen and about 1 mole of BF; per mole ofhydrate water pres- 13. The process of claim 11 wherein said free-BF entin said salt and (b) boron trifluoride in an amount ethylene weightratio is between about 0.35 and 1. such that the weight ratio of free-8Pto ethylene charged is at least about 0.2, removing product hydrocarbonReferences cued the file of i patent mixture containing alkylate productfrom said contacting 5 UNITED STATES PATENTS zone and separatingalkylate hydrocarbon product om 2,376,119 Brunet et al May 15, 1945unreacted isobutane and ethylene.

12. The process of claim ll wherein said temperature FOREIGN PATENTS isbetween about 25 C. and 40 C. 327,382 Great Britain Mar. 28, 1930

1. AN ALKYLATION PROCESS COMPRISING CONTACTING (A) AN ALKYLATABLE FEEDHYDROCARBON FROM THE CLASS CONSISTING OF (1) ISOPARAFFIN HAVING FROM 4TO 8 CARBON ATOMS AND (2) AROMATIC HYDROCARBON AND (B) AN OLEFIN HAVINGFROM 2 TO 12 CARBON ATOMS, IN THE PRESENCE OF A CATALYST COMPRISINGESSENTIALLY (I) A METAL PYROANTIMONATE SALT CONTAINING WATER OFHYDRATION, THE METAL ION OF SAID SALT BEING FORM THE CLASS CONSISTING OFCADMIUM, FERRIC, MAGNESIUM, MERCURY, NICKELOUS AND POTASSIUM DIHYDROGENAND (II) BF3, SAID BF3 BEING PRESENT IN AN AMOUNT IN EXCESS OF ABOUT 1MOLE PER MOLE OF WATER OF HYDRATION IN SAID SALT, AT A TEMPERATUREBETWEEN ABOUT -30*C. AND A TEMPERATURE SUSTANTIALLY BELOW THETEMPERATURE AT WHICH SAID HYDRATE SALT DECOMPOSES, AND AT A PRESSURESUFFICIENT TO MAINTAIN A SUBSTANTIAL PORTION OF SAID REACTANTS IN THELIQUID STATE, AND SEPERATING A HYROCARBON PRODUCT MIXTURE CONTAININGALKYLATE PRODUCT OF SAID FEED HYDROCARBON AND SAID OLEFIN.